Patent GB-883943-A (GB)
Title: Bis-ketenes and method of preparation
IPC: C07C57/38
Filed: 1958-03-07
Abstract: Bis-ketenes in which each ketene group is attached to a nuclear carbon atom of at least one aromatic hydrocarbon group and in which each ketene group is spaced from the other by a bridging group containing at least two carbon atoms which prevents interaction between the ketene groups (see Group IV(b)) may be homopolymerized, polymerized with polyols and polyamines or used as chain extenders for hydroxy- or amino-terminated polymers or as cross linking agents for polyvinyl alcohols.  In Examples: (1) anthraquinoketene of formula <FORM:0883943/IV (a)/1> is polymerized in the presence of oxygen to give a yellow material; (2) anthraquinoketene is refluxed with ethylene glycol, decamethylene glycol or hydroquinone in benzene and the benzene distilled off to give polyesters.  Reaction of anthraquinoketene with diamines (e.g. ethylene diamine) giving polyamides, aminoalcohols, (e.g. ethanolamine) giving polyester polyamides, dimercaptans giving polythioesters, urea giving polysecondary amides and dicarbamates giving polyallophanates.ALSO:The invention comprises bis-ketenes in which each ketene group is attached to a nuclear carbon atom of at least one aromatic hydrocarbon group and in which each ketene group is spaced from the other by a bridging group (i.e. a hydrocarbon group containing at least two carbon atoms and which prevents interaction between the ketene groups).  The bridging group may be aliphatic aromatic or cycloaliphatic or may comprise mixed aliphatic, aromatic and cycloaliphatic units.  They are prepared by dehydrohalogenating a bis-carboxylic acid halide derived from a suitably constituted dicarboxylic acid.  Many bis-carboxylic acid halides and final products are specified by means of formulae.  The bis-ketenes may be used to form polymers (see Group IV(a)).  In Examples: (1) 9 : 10-dihydroanthracene-9 : 10-dicarboxylic acid chloride is treated with triethylamine in benzene solution in a nitrogen atmosphere to give the bis-ketene of formula <FORM:0883943/IV (b)/1> which treated with potassium permanganate in acetone gives anthraquinone and when reacted with methanol or aniline gives the corresponding dimethyl ester and dianilide and when homopolymerised, the polymer dissolved in aqueous sodium hydroxide and acidified gives anthracene-9 : 10-dicarboxylic acid; (2) the chlorides of b  : b -p-phenylene - bis (alphaphenyl - propionic acid), a  : a 1-p-phenylene-bis (alphaphenyl acetic acid) and 1 : 4-dihydro-1 : 4-dicarboxy-naphthalene are converted to the corresponding ketenes as in (1) using ether instead of benzene in some cases.  9 : 10-dihydroanthracene-9 : 10-dicarboxylic acid chloride is prepared by reacting sodium with anthracene in diethyl ether under nitrogen to give sodio-anthracene, carbon dioxide is passed into the mixture, the sodium salt of the dicarboxylic acid separated, 9 : 10-dihydroanthracene-9 : 10-dicarboxylic acid precipitated from a solution of the salt and treated with phosphorus pentachloride in benzene.  a  : a 1-p-phenylene-bis (alphaphenylacetic acid) chloride and 1 : 4-dihydroxy-naphthalene-1 : 4-dicarboxylic acid chloride are similarly prepared from p-dibenzyl-benzene and naphthalene.  b  : b 1-p-phenylene-bis (alphaphenylpropionyl chloride) is prepared by reacting 2 mols of diethyl phenylmalonate with p-xylylene di-iodide in the presence of potassium isopropoxide hydrolysing and decarboxylating the tetra-acid so obtained with aqueous potassium hydroxide, acidifying the solution to give b  : b 1-p-phenylene-(alphaphenylpropionic acid) and treating this with phosphorus pentachloride.  Para-dibenzyl-benzene is prepared by reacting a benzoylchloride-aluminium chloride complex with diphenylmethane in carbon disulphide to give p-benzoyldiphenylmethane and heating the hydrazone thereof with potassium hydroxide.